CN106700083B - A kind of polyquaternary amine base glucose polydimethylsiloxane polyether and preparation method thereof and hand feel finishing agent - Google Patents
A kind of polyquaternary amine base glucose polydimethylsiloxane polyether and preparation method thereof and hand feel finishing agent Download PDFInfo
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- CN106700083B CN106700083B CN201611051778.0A CN201611051778A CN106700083B CN 106700083 B CN106700083 B CN 106700083B CN 201611051778 A CN201611051778 A CN 201611051778A CN 106700083 B CN106700083 B CN 106700083B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Abstract
Invention provides a kind of hand feel finishing agent of polyquaternary amine base glucose polydimethylsiloxane polyether and its preparation method and application the polyquaternary amine base polyethers dimethyl silicone polymer.The polyquaternary amine base glucose polydimethylsiloxane polyether is indicated with general formula I.It is selected by synthesis technology route and starting material, so that the apparent state of film forming of hand feel finishing agent of the present invention from currently available technology liquid or hemicolloid state be transformed into solid-state or elastomer solid-state, after revolutionizing previous organic silicon emulsion arrangement, fabric sense of touch " oiliness " is overweight, so that unnatural, the uncomfortable technical problem of " viscous hand " personal clothing.Therefore, hand feel finishing agent of the present invention imparts the new sense of touch of fabric again: dry and comfortable tack-free, dry and comfortable, natural fine and smooth pro-skin, silk quality are soft and smooth, at the same assign cotton fiber fabric moment it is hydrophilic, without hot xanthochromia, the beneficial function such as no phenol xanthochromia.
Description
Technical field
The present invention relates to textile function finishing agent field, in particular to a kind of polyquaternary amine base glucose polydimethylsiloxanes
Alkane polyethers and preparation method thereof and hand feel finishing agent.
Background technique
Currently, four developing stage of global textile organosilicon material development experience:
First stage be hydroxy-silicone-oil emulsion and methyl-silicone oil emulsion, its structural features are as follows:
Hydroxy silicon oil:Wherein n=1~100000；
Methyl-silicone oil:Wherein m=1~100000.
Second stage is amino-silicone lotion, its structural features are as follows:
Wherein: m=1~10000；N=1~50；R1=-C3H6NH2,-C3H6NHC2H4NH2。
Phase III be polyether silicone oil and polyether-modified amino-silicone, its structural features are as follows:
Polyether silicone oil:
Wherein m=1~100000, n=1~50；R2=-C3H6O-(C3H6O)a-(C2H4O)bA=2~10-H；B=5~
50；
Polyether-modified amino-silicone: MM sealing end
Wherein m=5~500；N=1~50；R3=-C3H6NH(C3H6O)a-(C2H4O)bA=2~10-H；B=5~50.
Fourth stage is amido polyether block silicone oil, its structural features are as follows:
Amido polyether block silicone oil:
Wherein a=1~20, b=1~60, m=1~250, p=1~100；R1=-CH3,-C2H5, C4H9,-H.
Applicant has carried out a large amount of research to the organosilicon material in aforementioned four stage, and obtains main listed by table 1
Each main performance for organosilicon material listed by contribution proportion and table 2 of the composition material to properties compares.
Contribution proportion of each main composition material of stage organosilicon material of table 1. to properties
The main performance of each stage organosilicon material of table 2. compares
Conclusion: it can be extracted according to table one, table two:
1. the silicone oil material from the first generation to forth generation is given to the contact sensing functions of fabric, mainly dimethyl silicone polymer
The chain link of high polymerIt is fluffy, soft, smooth to realize by the molecular size range for controlling PolydimethylsiloxaneChain Chain section
Equal contact sensing functions, however this chain link high polymer does not have ionic, by introducing amido cation group, improves the absorption of polymer
Amount changes its oriented attachment behavior, promotes contact sensing functions, dimethyl silicone polymerThis polymer does not have hydrophily, does not have
There is hot xanthochromia, without phenol xanthochromia.
2. the introducing of the polyethers of third generation silicone oil and polyether-modified amido, compared with second generation amino-silicone, contact sensing functions
It is not promoted, is declined instead, merely add the hydrophily of dimethyl silicone polymer, main cause is the molecular weight of third generation silicone oil
Very little, overall molecule amount is 5000~20000 or so, PolydimethylsiloxaneChain Chain sectionMolecular weight about 370~
7000, simultaneously because the introducing of polyethers destroys the film forming of PolydimethylsiloxaneChain Chain section.Review poly- diformazan in amino-silicone
Radical siloxane chain linkMolecular weight about 5000~40000 or so, film forming is interference-free.Third generation silicone oil is poly-
The introducing of ether or polyether-modified amido contributes bulkiness sense of touch.
3. the PolydimethylsiloxaneChain Chain section of forth generation silicone oil is the activated monomer being separately synthesized, i.e. α, ω-glycidyl
Aoxidize propyl dimethyl silicone polymer, structural formula are as follows:
WhereinThe molecular weight of PolydimethylsiloxaneChain Chain section can accomplish 15000 or so by acid balance catalysis method,
It can accomplish 80000 or so by the soda balance catalysis method that our company invents, it can be suitable with amino-silicone.
Wherein the amido polyethers of forth generation silicone oil is and α, ω-glycidyl aoxidize the linear phase of propyl dimethyl silicone polymer
Connection, amido polyethers pass through after linearly connected to the effect of film formation very little of PolydimethylsiloxaneChain Chain section, in amido cation
Under oriented attachment is theoretical, in most cases, not only the film forming of PolydimethylsiloxaneChain Chain section is not influenced, is helped instead
Help it is bigger, therefore table one, table two experimental data in, the finishing effect of forth generation silicone oil is more preferable than second generation amino-silicone,
It is exactly best evidence.
Wherein R1=-CH3,-C2H5,-C4H9,-H；A=1~20, b=1~40.
The amido polyethers that the forth generation silicone oil introduces from table one, table two experimental data it is found that its to bulkiness sense of touch
It contributes larger, flexibility, flatness is contributed little.So the sense of touch contribution of forth generation silicone oil mostlys come from poly dimethyl silicon
Oxygen alkane chain link.Thus its " oiliness " sense of touch still can not solve.
4. from the first generation to forth generation silicone oil, we summarize and learn, the sense of touch style 90%- for organosilicon material of weaving at present
99% contribution comes from PolydimethylsiloxaneChain Chain section, therefore all has apparent " oiliness " from the first generation to forth generation silicone oil.
As everybody living standard increasingly improves, back to nature, natural sense of touch are required to the sense of touch of fabric in the market.Cause
Fabric " oiliness " feel characteristics after this organosilicon material arranges are very prominent, personal clothing comfort shortcoming.
It would therefore be desirable to a kind of new hand feel finishing agent, with solve presently, there are arrangement behind material there is obvious " oil
The technical issues of property " sense of touch.
Summary of the invention
The purpose of the present invention is to provide a kind of polyquaternary amine base glucose polydimethylsiloxane polyethers and preparation method thereof
With the hand feel finishing agent using the polyquaternary amine base glucose polydimethylsiloxane polyether.In polyquaternary amine base Portugal of the invention
In grape sugar polydimethylsiloxane polyether and its hand feel finishing agent, by the way that glucose methylamine is introduced PolydimethylsiloxaneChain Chain section
In, so that the sense of touch style of high polymer brings very big change.Five hydroxyls of glucose methylamine are at normal temperature, independent first
Film forming ability is very strong, and film formed by glucose methylamine is solid film, and the volume of yarn can be made to become larger, and has fabric significant fluffy
Sense, the dimethyl silicone polymer with liquid polymer, the fluffy sense for being formed by film offer be not completely identical；Glucose methylamine institute
The solid film of formation, dry and comfortable, silk quality is smooth, fine and smooth soft pro-skin, slippery is very natural, naturally, absolutely tack-free, certainly and greatly
The flatness that the PolydimethylsiloxaneChain Chain section of molecular weight provides has very big difference.
In addition, the present invention is polyquaternary amine base glucose polyether silicon using the PolydimethylsiloxaneChain Chain section of small-molecular-weight
The pliability of the intramolecular of appropriateness is provided, the rigidity of intramolecular is reduced, to meet suitable wearability, while also being provided certain
Tactile softness.
In order to obtain above-mentioned purpose, present invention firstly provides a kind of polyquaternary amine base glucose polydimethylsiloxane polyether,
Following general formula I is indicated:
Wherein, A-Selected from Cl-, Br-, I-, CH3COO-, C2H5COO-, C3H7COO-Or one of laurate；N be selected from
10~1000 integer；A is the integer selected from 1~20；M is the integer selected from 2~100.
The present invention also provides the preparation method of above-mentioned polyquaternary amine base glucose polydimethylsiloxane polyether, the method packets
Include following steps:
Step 1. with 1,1,3,3- tetramethyldihydrogendisiloxane and allyl glycidyl ether for starting material, with chloroplatinic acid
Aqueous isopropanol be catalyst, under the conditions of 70 DEG C~80 DEG C react with obtain 1,3- glycidyl oxidation two silicon oxygen of propyl
Alkane；
The 1,3- glycidyl that step 2. is obtained with step 1 aoxidizes disiloxane and octamethylcy-clotetrasiloxane is
Beginning object, using tetramethylammonium hydroxide as catalyst, under nitrogen protection under the conditions of 80~155 DEG C reaction to obtain α, ω-epoxy
Propyl aoxidizes propyl dimethyl silicone polymer；
The α that step 3. is obtained with step 2, ω-glycidyl oxidation propyl dimethyl silicone polymer and glucose methylamine are
Starting material, in the presence of isopropanol, reaction is under the conditions of 60~85 DEG C of temperature to obtain α, the ω-different hydroxypropyl of methylamino glucose
Aoxidize propyl dimethyl silicone polymer；
The different hydroxypropyl of the α that step 4. is obtained to step 3, ω-methylamino glucose aoxidizes propyl polydimethylsiloxanes
After acid is added in alkane, α is added, ω-glycidyl polyethers reacts under the conditions of 60~85 DEG C in the presence of isopropanol, obtains mesh
Mark product polyquaternary amine base glucose polydimethylsiloxane polyether.
In an embodiment of the present invention, in the step 1, described 1,1,3,3- tetramethyldihydrogendisiloxane and allyl
The molar ratio range of base glycidol ether is in 1:(2.1~4.0) between；The dosage of the catalyst is step 1 reaction system
The 0.05%~0.1% of gross mass；Also, the mass percentage concentration of the aqueous isopropanol of the chloroplatinic acid as catalyst is
1%.
In an embodiment of the present invention, in the step 2,1, the 3- glycidyl aoxidizes disiloxane and eight
The quality of methyl cyclotetrasiloxane is than range in (34~90): between 1000；The dosage of the tetramethylammonium hydroxide is step
The 0.05%~0.1% of rapid 2 reaction system gross mass.
In an embodiment of the present invention, in the step 3, the α, ω-glycidyl aoxidize propyl poly dimethyl silicon
The molar ratio range of oxygen alkane and glucose methylamine is in 1.0:(2.0~2.2)；The dosage of the isopropanol is step 3 reactant
It is the 40%~70% of gross mass.
In an embodiment of the present invention, in the step 4, the different hydroxypropyl oxidation third of the α, ω-methylamino glucose
Base dimethyl silicone polymer and α, ω-glycidyl polyethers molar ratio range is in (0.5~2): 1；The isopropanol adds
Amount is the 40%~70% of step 4 reaction system gross mass；The dosage of the acid be and the α, ω-glycidyl polyethers
Molal weight is equal；The dosage of the isopropanol is the 40%~70% of step 4 reaction system gross mass.Preferably, described
Acid is selected from HCl, HBr, HI, CH3COOH、CH3CH2COOH、CH3C2H4One of COOH or lauric acid.
In a preferred embodiment of the present invention, the preparation of above-mentioned polyquaternary amine base glucose polydimethylsiloxane polyether is provided
Method the described method comprises the following steps:
Step 1. with 1,1,3,3- tetramethyldihydrogendisiloxane and allyl glycidyl ether for starting material, by described 1,
1,3,3- tetramethyldihydrogendisiloxane and allyl glycidyl ether are 1:(2.1~4.0 according to molar ratio) ratio mix,
And using the aqueous isopropanol that mass percentage concentration is 1% chloroplatinic acid as catalyst, reaction is under the conditions of 70 DEG C~80 DEG C to obtain
1,3- glycidyl aoxidizes disiloxane；
The 1,3- glycidyl that step 2. is obtained with step 1 aoxidizes disiloxane and octamethylcy-clotetrasiloxane is
Beginning object, using tetramethylammonium hydroxide as catalyst, under nitrogen protection under the conditions of 80~155 DEG C reaction to obtain α, ω-epoxy
Propyl aoxidizes propyl dimethyl silicone polymer；Wherein, 1, the 3- glycidyl oxidation disiloxane and prestox ring four
The quality of siloxanes is than range in (34~90): between 1000；The dosage of the tetramethylammonium hydroxide is step 2 reactant
It is the 0.05%~0.1% of gross mass；
The α that step 3. is obtained with step 2, ω-glycidyl oxidation propyl dimethyl silicone polymer and glucose methylamine are
Starting material, in the presence of isopropanol, reaction is under the conditions of 60~85 DEG C of temperature to obtain α, the ω-different hydroxypropyl of methylamino glucose
Aoxidize propyl dimethyl silicone polymer；Wherein, the α, ω-glycidyl oxidation propyl dimethyl silicone polymer and glucose first
The molar ratio range of amine is in 1.0:(2.0~2.2)；The dosage of the isopropanol is the 40% of step 3 reaction system gross mass
~70%；
The different hydroxypropyl of the α that step 4. is obtained to step 3, ω-methylamino glucose aoxidizes propyl polydimethylsiloxanes
After acid is added in alkane, α is added, ω-glycidyl polyethers reacts under the conditions of 60~85 DEG C in the presence of isopropanol, obtains mesh
Mark product polyquaternary amine base glucose polydimethylsiloxane polyether；Wherein, the different hydroxypropyl oxidation of the α, ω-methylamino glucose
Propyl dimethyl silicone polymer and α, ω-glycidyl polyethers molar ratio range is in (0.5~2): 1；The throwing of the isopropanol
Dosage is the 40%~70% of step 4 reaction system gross mass；The dosage of the acid be and the α, ω-glycidyl polyethers
Molal weight it is equal；Also, the dosage of the isopropanol is the 40%~70% of step 4 reaction system gross mass.
In a preferred embodiment, the acid is selected from HCl, HBr, HI, CH3COOH、CH3CH2COOH、
CH3C2H4One of COOH or lauric acid.
In an embodiment of the present invention, further include the steps that removing unreacted reactant and removing in 1~step 4 of above-mentioned steps
Isopropanol step, for example, the step 1 further include: in 140 DEG C~180 DEG C vacuum degree -0.1~-0.095Mpa, temperature conditions
The lower unreacted allyl glycidyl ether of removing；The step 2 further include: in vacuum degree -0.1~-0.095Mpa, temperature
Unreacted octamethylcy-clotetrasiloxane ex hoc genus anne object is removed under the conditions of 140 DEG C~160 DEG C；And the step 4 is also wrapped
It includes: the step of 85~120 DEG C of distillation isopropanols.
In an embodiment of the present invention, the reaction time of the step 1 is 4~12 hours；In the step 2, first exist
It reacts 8~48 hours under the conditions of 80~110 DEG C, then, then reacts 2~5 hours under the conditions of 135~155 DEG C；It is described not walk 3
Reaction time be 12~48 hours；The reaction time of the step 4 is 12~60 hours.
Therefore, in a preferred embodiment of the present invention, above-mentioned polyquaternary amine base glucose polydimethylsiloxane polyether is provided
Preparation method, the described method comprises the following steps:
Step 1. with 1,1,3,3- tetramethyldihydrogendisiloxane and allyl glycidyl ether for starting material, by described 1,
1,3,3- tetramethyldihydrogendisiloxane and allyl glycidyl ether are 1:(2.1~4.0 according to molar ratio) ratio mix,
And using the aqueous isopropanol that mass percentage concentration is 1% chloroplatinic acid as catalyst, it is small that 4~12 are reacted under the conditions of 70 DEG C~80 DEG C
Shi Hou removes unreacted allyl glycidol under the conditions of vacuum degree -0.1~-0.095Mpa, 140 DEG C~180 DEG C of temperature
Ether obtains 1,3- glycidyl and aoxidizes disiloxane；
The 1,3- glycidyl that step 2. is obtained with step 1 aoxidizes disiloxane and octamethylcy-clotetrasiloxane is
Beginning object under nitrogen protection, first reacts 8~48 hours under the conditions of 80~110 DEG C using tetramethylammonium hydroxide as catalyst,
Then, after then being reacted 2~5 hours under the conditions of 135~155 DEG C, vacuum degree -0.1~-0.095Mpa, 140 DEG C of temperature~
Unreacted octamethylcy-clotetrasiloxane ex hoc genus anne object is removed under the conditions of 160 DEG C, obtains α, and ω-glycidyl oxidation propyl is poly-
Dimethyl siloxane；Wherein, the mass ratio of the oxidation of 1,3- the glycidyl disiloxane and octamethylcy-clotetrasiloxane
Range is in (34~90): between 1000；The dosage of the tetramethylammonium hydroxide is step 2 reaction system gross mass
0.05%~0.1%；
The α that step 3. is obtained with step 2, ω-glycidyl oxidation propyl dimethyl silicone polymer and glucose methylamine are
Starting material after reacting 12~48 hours under the conditions of 60~85 DEG C of temperature, obtains α, ω-methylamino Portugal in the presence of isopropanol
The different hydroxypropyl of grape sugar aoxidizes propyl dimethyl silicone polymer；Wherein, the α, ω-glycidyl aoxidize propyl polydimethylsiloxanes
The molar ratio range of alkane and glucose methylamine is in 1.0:(2.0~2.2)；The dosage of the isopropanol is step 3 reaction system
The 40%~70% of gross mass；
The different hydroxypropyl of the α that step 4. is obtained to step 3, ω-methylamino glucose aoxidizes propyl polydimethylsiloxanes
After acid is added in alkane, α, ω-glycidyl polyethers are added, in the presence of isopropanol, 12~60 are reacted under the conditions of 60~85 DEG C
After hour, isopropanol is distilled out under the conditions of 80~120 DEG C, obtains target product polyquaternary amine base glucose dimethyl silicone polymer
Polyethers；Wherein, the different hydroxypropyl oxidation propyl dimethyl silicone polymer of the α, ω-methylamino glucose and α, ω-glycidyl
The molar ratio range of polyethers is in (0.5~2): 1；The dosage of the isopropanol be step 4 reaction system gross mass 40%~
70%；The dosage of the acid be with the α, ω-glycidyl polyethers molal weight is equal；Also, the isopropanol
Dosage is the 40%~70% of step 4 reaction system gross mass.
The present invention also provides a kind of hand feel finishing agent, the effective component of the hand feel finishing agent is described in claim 1
Polyquaternary amine base glucose polydimethylsiloxane polyether.
In an embodiment of the present invention, the hand feel finishing agent includes by mass percentage: 30~40% poly- season
Ammonium glucose polydimethylsiloxane polyether；68~46% nonionic emulsifier；0.01~0.05% acetic acid；Surplus is
Water；Also, the pH value value range of the hand feel finishing agent is between 4.5~6.5.
In an embodiment of the present invention, the nonionic emulsifier is isomeric alcohol polyethenoxy ether, with following general formula: CH3
(CHCH3)a(CH2)bO(C2H4O)cH is indicated；Wherein, a=1~4, b=1~10, c=3~20.Preferably, the nonionic
Emulsifier is selected from isomery C8 alcohol polyoxyethylene ether, one of isomery C10 alcohol polyoxyethylene ether or isomery C13 alcohol polyoxyethylene ether
Or several mixing.
In the polyquaternary amine base glucose polydimethylsiloxane polyether of the invention and its hand feel finishing agent, pass through by
Glucose methylamine is introduced into PolydimethylsiloxaneChain Chain section, so that the sense of touch style of high polymer brings very big change.First
At normal temperature, independent film forming ability is very strong for five hydroxyls of glucose methylamine, and film formed by glucose methylamine is solid film, can make
The volume of yarn becomes larger, and fabric is made to have significant fluffy sense, the dimethyl silicone polymer with liquid polymerIt is formed
Film provide fluffy sense it is completely not identical；Glucose methylamine is formed by solid film, dry and comfortable, silk quality is smooth, fine and smooth soft parent
Skin, slippery are very natural, naturally, absolutely tack-free, are provided certainly with the PolydimethylsiloxaneChain Chain section of macromolecule smooth
Property has very big difference.
In addition, the present invention is polyquaternary amine base glucose polyether silicon using the PolydimethylsiloxaneChain Chain section of small-molecular-weight
The pliability of the intramolecular of appropriateness is provided, the rigidity of intramolecular is reduced, to meet suitable wearability, while also being provided certain
Tactile softness.
In the present invention, it is selected by synthesis technology route and starting material, so that hand feel finishing agent of the present invention
The apparent state that forms a film from currently available technology liquid or hemicolloid state be transformed into solid-state or elastomer solid-state, to thoroughly change
After having become previous organic silicon emulsion arrangement, fabric sense of touch " oiliness " is overweight, so that " viscous hand " personal clothing is unnatural, it is uncomfortable
Technical problem.Therefore, hand feel finishing agent of the present invention imparts the new sense of touch of fabric again: dry and comfortable tack-free, dry and comfortable, day
So exquisiteness pro-skin, silk quality is soft and smooth, at the same assign cotton fiber fabric moment it is hydrophilic, without hot xanthochromia, the beneficial function such as no phenol xanthochromia.
Product of the present invention improves the surcharge of fabric.Product of the present invention has been achieved with large-scale technology production.
Specific embodiment
Hereinafter, technology of the invention is described in detail in conjunction with specific embodiment.It is appreciated that the various following tool
Body embodiment is only used for helping skilled in the art to understand the present invention, rather than limitation of the present invention.
A kind of polyquaternary amine base glucose polydimethylsiloxane polyether of embodiment 1.
In the present embodiment, a kind of polyquaternary amine base glucose polydimethylsiloxane polyether is provided.Polyquaternary amine base Portugal
Grape sugar polydimethylsiloxane polyether is indicated with following general formula I:
Wherein, A-Selected from Cl-, Br-, I-, CH3COO-, C2H5COO-, C3H7COO-Or one of laurate；N be selected from
10~1000 integer；A is the integer selected from 1~20；M is the integer selected from 2~100.
The preparation method of above-mentioned polyquaternary amine base glucose polydimethylsiloxane polyether is specific as follows:
Step 1. with 1,1,3,3- tetramethyldihydrogendisiloxane and allyl glycidyl ether for starting material, by described 1,
1,3,3- tetramethyldihydrogendisiloxane and allyl glycidyl ether are 1:(2.1~4.0 according to molar ratio) ratio mix,
And using the aqueous isopropanol that mass percentage concentration is 1% chloroplatinic acid as catalyst, amount used in the catalyst is reactant
It is the 0.05%~0.1% of total weight, catalyst is added portionwise at 45~85 DEG C of temperature, is reacted under the conditions of 70 DEG C~80 DEG C
After 4~12 hours, through infrared chromatography detection SiH characteristic peak disappear after, vacuum degree -0.1~-0.095Mpa, 140 DEG C of temperature~
Unreacted allyl glycidyl ether is removed under the conditions of 180 DEG C, is obtained 1,3- glycidyl and is aoxidized disiloxane；
Reaction equation described above are as follows:
The 1,3- glycidyl that step 2. is obtained with step 1 aoxidizes disiloxane and octamethylcy-clotetrasiloxane is
Beginning object under nitrogen protection, first reacts 8~48 hours under the conditions of 80~110 DEG C using tetramethylammonium hydroxide as catalyst,
Then, after then being reacted 2~5 hours under the conditions of 135~155 DEG C, vacuum degree -0.1~-0.095Mpa, 140 DEG C of temperature~
Unreacted octamethylcy-clotetrasiloxane ex hoc genus anne object is removed under the conditions of 160 DEG C, obtains α, and ω-glycidyl oxidation propyl is poly-
Dimethyl siloxane；Wherein, the mass ratio of the oxidation of 1,3- the glycidyl disiloxane and octamethylcy-clotetrasiloxane
Range is in (34~90): between 1000；The dosage of the tetramethylammonium hydroxide is step 2 reaction system gross mass
0.05%~0.1%；
Obtained α, ω-glycidyl oxidation propyl polydimethylsiloxane structural are as follows:
Wherein m=10~1000；
Reaction equation described above are as follows:
The α that step 3. is obtained with step 2, ω-glycidyl oxidation propyl dimethyl silicone polymer and glucose methylamine are
Starting material after reacting 12~48 hours under the conditions of 60~85 DEG C of temperature, obtains α, ω-methylamino Portugal in the presence of isopropanol
The different hydroxypropyl of grape sugar aoxidizes propyl dimethyl silicone polymer；Wherein, the α, ω-glycidyl aoxidize propyl polydimethylsiloxanes
The molar ratio range of alkane and glucose methylamine is in 1.0:(2.0~2.2)；The dosage of the isopropanol is step 3 reaction system
The 40%~70% of gross mass；
The structure of the glucose methylamine is as follows:
Reaction equation described above are as follows:
Wherein n=10~1000；And
The different hydroxypropyl of the α that step 4. is obtained to step 3, ω-methylamino glucose aoxidizes propyl polydimethylsiloxanes
After acid is added in alkane, α, ω-glycidyl polyethers are added, in the presence of isopropanol, 12~60 are reacted under the conditions of 60~85 DEG C
After hour, isopropanol is distilled out under the conditions of 80~120 DEG C, obtains target product polyquaternary amine base glucose dimethyl silicone polymer
Polyethers；Wherein, the different hydroxypropyl oxidation propyl dimethyl silicone polymer of the α, ω-methylamino glucose and α, ω-glycidyl
The molar ratio range of polyethers is in (0.5~2): 1；The dosage of the isopropanol be step 4 reaction system gross mass 40%~
70%；The dosage of the acid be with the α, ω-glycidyl polyethers molal weight is equal；Also, the isopropanol
Dosage is the 40%~70% of step 4 reaction system gross mass；
Wherein, the α, ω-glycidyl polyethers structure are as follows:
Wherein a=1~20, b=1~60；
Reaction equation described above are as follows:
Wherein, A-=Cl-、Br-、I-、CH3COO-、C2H5COO-、C3H7COO-Or one of cinnamic acid root；Also, n=10
~1000, a=1~20, b=1~60, m=2~100.
A kind of hand feel finishing agent of embodiment 2.
In the present embodiment, a kind of hand feel finishing agent is provided, the hand feel finishing agent includes by mass percentage: 30~
The polyquaternary amine base glucose polydimethylsiloxane polyether made from 40% embodiment 1；68~46% non-ionic emulsifier
Agent；0.01~0.05% acetic acid；Surplus is water；Also, the pH value value range of the hand feel finishing agent is between 4.5~6.5.
The nonionic emulsifier is isomeric alcohol polyethenoxy ether, with following general formula: CH3(CHCH3)a(CH2)bO
(C2H4O)cH is indicated；Wherein, a=1~4, b=1~10, c=3~20.Preferably, the nonionic emulsifier is selected from isomery
C8 alcohol polyoxyethylene ether, the mixing of one or more of isomery C10 alcohol polyoxyethylene ether or isomery C13 alcohol polyoxyethylene ether.
The preparation method of above-mentioned hand feel finishing agent is specific as follows.
The polyquaternary amine base glucose polydimethylsiloxane polyether and the nonionic emulsifier that embodiment 1 is obtained
It is uniformly mixed, is then slowly diluted with water, second acid for adjusting pH is finally used, so that the pH value of the hand feel finishing agent finally obtained
Between 4.5~6.5.
The performance test of hand feel finishing agent described in 3. embodiment 2 of embodiment
In the present embodiment, the research of filming performance has been carried out to the hand feel finishing agent obtained of embodiment 2.
It has been found that the senses of touch style such as " dry and comfortable, natural fine and smooth pro-skin, silk quality are soft and smooth " mainly from: in polymer point
Glucose methylamine chain link is introduced in minor structure, independent film forming ability is very strong at normal temperature for glucose methylamine, in high polymer poly- season
In the different hydroxypropyl oxidation propyl polydimethylsiloxane polyether molecule of ammonium glucose, two sections of adjacent polyquaternary amine base grape sugar chains
Section forms the very bright and clean solid film in very well ordered, fine and close, surface, sense of touch slippery is very unique after high temperature dehydration.
Therefore, in the present embodiment, first by the way that in the baking of glass surface ware, (105 DEG C -110 DEG C of temperature, baking 2-3 is small
When) film obtained by product lotion, the final filming performance of observational study different type silicone oil.
Experiment condition specifically: glass surface ware, diameter 8cm, 105 DEG C~110 DEG C of oven temperature, the time 2.5 hours, cream
Liquid solid content is 45% or so, toasts lotion weight: 5g.Experimental result is see table 1.
The performance comparison of 1. second generation of table, forth generation and hand feel finishing agent of the present invention
In addition, applicant is also with 32s, the 40s looped fabric of combed cotton containing spandex thread is experimental subjects, product emulsion solid content
It is 45%, dosage 80g/l, pick-up 80%, 190 DEG C of setting temperature, speed 40m/min, retention time 40 seconds, after sizing sufficiently
Resurgence 2 hours, hydrophily, the feel of the cloth specimen after the test second generation, forth generation and hand feel finishing agent of the present invention arrangement are commented
It is fixed, yellowing-resistant, anti-phenol xanthochromia are tested, and obtain 2~table of table, 4 data.
Cloth specimen fluffy degree comparison of the table 2. after the second generation, forth generation and hand feel finishing agent of the present invention arrangement
Cloth specimen pliability comparison of the table 3. after the second generation, forth generation and hand feel finishing agent of the present invention arrangement
Cloth specimen smoothness comparison of the table 4. after the second generation, forth generation and hand feel finishing agent of the present invention arrangement
Conclusion: it can be obtained from the experimental result of above-mentioned 1~table of table 4:
A, film formed by amino-silicone is the film of liquid or semi liquid state oiliness, is compared through its cunning property of fabric after arranging
Weight when dosage is larger, there is significant " viscous hand " sense, the comfort shortcoming of personal clothing.
B, film formed by amido polyether block silicone oil is liquid or semi-liquid film, through its greasy ratio of fabric after arranging
Amino-silicone is slightly light.When dosage is larger, also there is significant " viscous hand " sense, the comfort of personal clothing is also short of.
C, the polymer emulsion of this invention, formed film is solid-state, the flexible film of the bright and clean lubrication of semisolid, through it
Fabric after arrangement, it is bright and clean dry and comfortable, it is tack-free, and also sense of touch is fine and smooth, and personal clothing is more natural comfortable.The material of this invention
It is the supplement of modified organic silicon material helps.
D, the material of this invention known to experiment one, experiment two has dry and comfortable, natural fine and smooth pro-skin, silk quality velvet touch
Style contact sensing functions, main cause be, the present invention introduced from single molecule structure one can change polysiloxanes chain link at
The specific links of membrane stage.--- polyquaternary amine base glucose chain link, it at -38 DEG C of ultralow temperature still be liquid polysiloxanes,
Become solid-state at normal temperature, fundamentally solves " viscous hand " sense of touch of polysiloxanes.
E, due to the superpower film forming ability of polyquaternary amine base glucose and the exclusive characteristic of formed film, fine and close, bright and clean,
The senses of touch such as mellow and full, dry and comfortable change " cunning " characteristic of polysiloxanes.
F, due to being solid or semisolid after the polymer film forming of this invention, the swelliong power of yarn is wanted
It is more more prominent than the fluffy sense that liquid/semi liquid state polymer generates.
G, learn from the experiment content of technical background table two: first generation silicone oil, hydroxy silicon oil and methyl-silicone oil are yellow without heat
Change and phenol xanthochromia, second generation amino-silicone, due to introducing primary amine groups (- NH in molecular structure2), secondary amine (- NRH) and produce
Hot xanthochromia and phenol xanthochromia；In third generation silicone oil, the difference of polyether silicone oil and polyether-modified amino-silicone, polyether silicone oil is without hot yellow
Become, no phenol xanthochromia obtains moment hydrophilicity；Polyether-modified amino-silicone, since the introducing of secondary amine (- NHR) produces
Hot xanthochromia and phenol xanthochromia, the hydrophily of acquisition are the hydrophilies of general grade, are not moment hydrophilies；Including forth generation silicone oil amine
Base polyether block introduces primary amine groups (- NH2), secondary amine (- NRH) also produces hot xanthochromia and phenol xanthochromia in experimental result.
This invention introduces tertiary amine groups, but the reaction result of process is all completely converted into quaternary ammonium group, therefore the polymerization of this invention
Object, without hot xanthochromia and phenol xanthochromia.
H, conclusion: quaternary ammonium group does not generate hot xanthochromia and phenol xanthochromia, primary amine groups (- NH2), secondary amine (- NRH) can generate hot Huang
Become, phenol xanthochromia.
I, this invention, which has been introduced, has the reactive hydrophilic α of height, ω-glycidyl polyethers, chemical structure are as follows:
Wherein a=1~20, b=1~60, the production of this invention
Product hydrophily speed can reach purpose by adjusting b parameter size and whole pfpe molecule amount size.
In addition, ω-glycidyl aoxidizes the poly- diformazan of propyl it has been found that obtaining the α in the present invention, in step 2
The structure of radical siloxane will will lead to performance in final products.The α, ω-glycidyl aoxidize propyl polydimethylsiloxanes
Alkane is as follows:
Wherein,
When 40≤n≤60, end objectives product is biased to fluffy；When 60≤n≤80, end objectives product is biased to soft；80
When≤n≤130, end objectives product is partial to smoothly.
1 fluff type product of Application Example
A kind of hand feel finishing agent is provided in the present embodiment, is fluff type product, specific preparation method is as follows.
Step (1) is 1% isopropyl alcohol solution of chloroplatinic acid as catalyst using concentration, to 1,1,3,3- tetramethyl dihydro, two silicon oxygen
Alkane and allyl glycidyl ether (wherein the molar ratio of the two is 1:2.1~4.0) mixture, in temperature 45 C~85 DEG C condition
Under be added portionwise, keep the temperature 70 DEG C~80 DEG C, soaking time 4 hours~12 hours, through infrared chromatography detection SiH characteristic peak disappear
Afterwards, in vacuum degree -0.1~-0.095Mpa, 140 DEG C~180 DEG C of the temperature unreacted allyl glycidyl ethers of removing must be produced
Object.
1,3- glycidyl disiloxaneThe chloroplatinic acid catalyst
Used amount is 0.05%~0.1% of weight in system, 1,1,3,3- tetramethyldihydrogendisiloxane and allyl glycidyl
The molar ratio of glycerin ether are as follows: 1:2.1~4.0.Reaction equation described above are as follows:
Step (2) is added to 1, the 3- glycidyl oxidation for obtaining step (1) using tetramethylammonium hydroxide as catalyst
In disiloxane and octamethylcy-clotetrasiloxane mixture, under the conditions of 80 DEG C~110 DEG C of temperature, 8~48 hours are kept the temperature
Later, under nitrogen protection, be warming up under the conditions of 135 DEG C~155 DEG C, keep the temperature 2~5 hours, then vacuum degree -0.1~-
0.095Mpa, 140 DEG C~160 DEG C of temperature unreacted octamethylcy-clotetrasiloxanes of removing ex hoc genus anne object, obtains product α, ω-ring
Oxygen propyl group aoxidizes propyl dimethyl silicone polymer, and structure is as follows:
Wherein m=50, the tetramethylammonium hydroxide dosage are 0.1~0.05% of weight in system；Described 1,
3- glycidyl aoxidizes disiloxane and octamethylcy-clotetrasiloxane weight ratio are as follows: 90:1000.Reactional equation described above
Formula are as follows:
Wherein m=50
The target product α that step (3) obtains step (2), ω-glycidyl oxidation propyl dimethyl silicone polymer are added
To in the mixture of glucose methylamine and isopropanol, the structure of glucose methylamine are as follows:
Under the conditions of 60~85 DEG C of temperature, react 12~48 hours.Obtain product α, the ω-different hydroxypropyl of methylamino glucose
Aoxidize propyl dimethyl silicone polymer, reaction equation are as follows:
It is 40~70% that wherein isopropanol, which accounts for the total weight of reaction system, the glucose methylamine and α, ω-glycidyl
The molar ratio for aoxidizing propyl dimethyl silicone polymer is 2.0~2.2:1.
The target product α of step (3), the different hydroxypropyl of ω-methylamino glucose are aoxidized propyl poly dimethyl silicon by step (4)
Oxygen alkane is added acid and is uniformly mixed, then add α, ω-glycidyl polyethers, in temperature 60 under the conditions of 20~60 DEG C of temperature
Under the conditions of~85 DEG C, reacts 12~60 hours, then distill out isopropanol under the conditions of 85 DEG C~120 DEG C of temperature, obtain target
Product: the different hydroxypropyl of polyquaternary amine base glucose aoxidizes propyl polydimethylsiloxane polyether.Wherein the acid is HCl, HBr,
HI, CH3COOH, CH3CH2COOH, CH3C2H4COOH, one or more of mixtures, the weight being added are grape to lauric acid in the middle
The equimolar quantity of sugared methylamine.The wherein α, ω-glycidyl polyethers structure feature are as follows:
Wherein a=2~6, b=15~40.It is above-mentioned anti-
Answer equation as follows:
Wherein A-=Cl-, Br-, I-, CH3COO-, C2H5COO-, C3H7COO-, laurate.
N=50, a=2~6, b=15~40, m=2~100.
The different hydroxypropyl oxidation propyl dimethyl silicone polymer of above-mentioned α, ω-methylamino glucose and α, ω-glycidyl are poly-
The molar ratio of ether is 2:3~3:4, and wherein isopropanol accounts for system total weight 40%~70%.
The different hydroxypropyl of the target product polyquaternary amine base glucose of step (4) is aoxidized propyl polydimethylsiloxanes by step (5)
Alkane polyethers is uniformly mixed with nonionic emulsifier isomeric alcohol polyethenoxy ether, is then slowly diluted with water, and is finally adjusted with acetic acid
PH value, makes pH value value between 4.5~6.5, and it is poly- then to obtain the different hydroxypropyl oxidation propyl of target product polyquaternary amine base glucose
Dimethyl siloxane polyethers hand feel finishing agent.The hand feel finishing agent includes specifically following components by mass percentage: 40%
Polyquaternary amine base glucose silicone polyether, 2.5% ten carbon isomery alcohol polyoxyethylene -5,2.5% ten carbon isomery alcohol it is poly-
The acetic acid that the concentration of ethylene oxide -9,0.5% is 100%, surplus is water.It is denoted as hand feel finishing agent A.
2 soft type product of Application Example
A kind of hand feel finishing agent is provided in the present embodiment, is soft type product, specific preparation method is as follows.
Case study on implementation B (soft type product)
Step (1) is 1% isopropyl alcohol solution of chloroplatinic acid as catalyst using concentration, to 1,1,3,3- tetramethyl dihydro, two silicon oxygen
Alkane and allyl glycidyl ether (wherein the molar ratio of the two is 1:2.1~4.0) mixture, in temperature 45 C~85 DEG C condition
Under be added portionwise, keep the temperature 70 DEG C~80 DEG C, soaking time 4 hours~12 hours, through infrared chromatography detection SiH characteristic peak disappear
Afterwards, in vacuum degree -0.1~-0.095Mpa, 140 DEG C~180 DEG C of the temperature unreacted allyl glycidyl ethers of removing must be produced
Object.
1,3- glycidyl disiloxaneThe chloroplatinic acid catalyst
Used amount is 0.05%~0.1% of weight in system, 1,1,3,3- tetramethyldihydrogendisiloxane and allyl glycidyl
The molar ratio of glycerin ether are as follows: 1:2.1~4.0.Reaction equation described above are as follows:
Step (2) is added to 1, the 3- glycidyl oxidation for obtaining step (1) using tetramethylammonium hydroxide as catalyst
In disiloxane and octamethylcy-clotetrasiloxane mixture, under the conditions of 80 DEG C~110 DEG C of temperature, 8~48 hours are kept the temperature
Later, under nitrogen protection, be warming up under the conditions of 135 DEG C~155 DEG C, keep the temperature 2~5 hours, then vacuum degree -0.1~-
0.095Mpa, 140 DEG C~160 DEG C of temperature unreacted octamethylcy-clotetrasiloxanes of removing ex hoc genus anne object, obtains product α, ω-ring
Oxygen propyl group aoxidizes propyl dimethyl silicone polymer, and structure is as follows:
Wherein m=80, the tetramethylammonium hydroxide dosage are 0.1~0.05% of weight in system；Described 1,
3- glycidyl aoxidizes disiloxane and octamethylcy-clotetrasiloxane weight ratio are as follows: 55:1000.Reactional equation described above
Formula are as follows:
Wherein m=80
The target product α that step (3) obtains step (2), ω-glycidyl oxidation propyl dimethyl silicone polymer are added
To in the mixture of glucose methylamine and isopropanol, the structure of glucose methylamine are as follows:
Under the conditions of 60~85 DEG C of temperature, react 12~48 hours.Obtain product α, the ω-different hydroxypropyl of methylamino glucose
Aoxidize propyl dimethyl silicone polymer, reaction equation are as follows:
It is 40~70% that wherein isopropanol, which accounts for the total weight of reaction system, the glucose methylamine and α, ω-glycidyl
The molar ratio for aoxidizing propyl dimethyl silicone polymer is 2.0~2.2:1.
The target product α of step (3), the different hydroxypropyl of ω-methylamino glucose are aoxidized propyl poly dimethyl silicon by step (4)
Oxygen alkane is added acid and is uniformly mixed, then add α, ω-glycidyl polyethers, in temperature 60 under the conditions of 20~60 DEG C of temperature
Under the conditions of~85 DEG C, reacts 12~60 hours, then distill out isopropanol under the conditions of 85 DEG C~120 DEG C of temperature, obtain target
Product: the different hydroxypropyl of polyquaternary amine base glucose aoxidizes propyl polydimethylsiloxane polyether.Wherein the acid is HCl, HBr,
HI, CH3COOH, CH3CH2COOH, CH3C2H4COOH, one or more of mixtures, the weight being added are grape to lauric acid in the middle
The equimolar quantity of sugared methylamine.The wherein α, ω-glycidyl polyethers structure feature are as follows:
Wherein a=2~6, b=15~40
Above-mentioned reaction equation is as follows:
Wherein A-=Cl-, Br-, I-, CH3COO-, C2H5COO-, C3H7COO-, laurate.
N=80, a=2~6, b=15~40, m=2~100.
The different hydroxypropyl oxidation propyl dimethyl silicone polymer of above-mentioned α, ω-methylamino glucose and α, ω-glycidyl are poly-
The molar ratio of ether is 3:4~4:5, and wherein isopropanol accounts for system total weight 40%~70%.
The different hydroxypropyl of the target product polyquaternary amine base glucose of step (4) is aoxidized propyl polydimethylsiloxanes by step (5)
Alkane polyethers is uniformly mixed with nonionic emulsifier isomeric alcohol polyethenoxy ether, is then slowly diluted with water, and is finally adjusted with acetic acid
PH value, makes pH value value between 4.5~6.5, and it is poly- then to obtain the different hydroxypropyl oxidation propyl of target product polyquaternary amine base glucose
Dimethyl siloxane polyethers hand feel finishing agent.The hand feel finishing agent includes specifically following components by mass percentage: 40%
Polyquaternary amine base glucose silicone polyether, 2.5% ten carbon isomery alcohol polyoxyethylene -5,2.5% ten carbon isomery alcohol it is poly-
The acetic acid that the concentration of ethylene oxide -9,0.5% is 100%, surplus is water.It is denoted as hand feel finishing agent B.
3 smooth type product of Application Example
A kind of hand feel finishing agent is provided in the present embodiment, is smooth type product, specific preparation method is as follows.
Step (1) is 1% isopropyl alcohol solution of chloroplatinic acid as catalyst using concentration, to 1,1,3,3- tetramethyl dihydro, two silicon oxygen
Alkane and allyl glycidyl ether (wherein the molar ratio of the two is 1:2.1~4.0) mixture, in temperature 45 C~85 DEG C condition
Under be added portionwise, keep the temperature 70 DEG C~80 DEG C, soaking time 4 hours~12 hours, through infrared chromatography detection SiH characteristic peak disappear
Afterwards, in vacuum degree -0.1~-0.095Mpa, 140 DEG C~180 DEG C of the temperature unreacted allyl glycidyl ethers of removing must be produced
Object.
1,3- glycidyl disiloxaneThe chloroplatinic acid catalyst
Used amount is 0.05%~0.1% of weight in system, 1,1,3,3- tetramethyldihydrogendisiloxane and allyl glycidyl
The molar ratio of glycerin ether are as follows: 1:2.1~4.0.Reaction equation described above are as follows:
Step (2) is added to 1, the 3- glycidyl oxidation for obtaining step (1) using tetramethylammonium hydroxide as catalyst
In disiloxane and octamethylcy-clotetrasiloxane mixture, under the conditions of 80 DEG C~110 DEG C of temperature, 8~48 hours are kept the temperature
Later, under nitrogen protection, be warming up under the conditions of 135 DEG C~155 DEG C, keep the temperature 2~5 hours, then vacuum degree -0.1~-
0.095Mpa, 140 DEG C~160 DEG C of temperature unreacted octamethylcy-clotetrasiloxanes of removing ex hoc genus anne object, obtains product α, ω-ring
Oxygen propyl group aoxidizes propyl dimethyl silicone polymer, and structure is as follows:
Wherein m=130, the tetramethylammonium hydroxide dosage are 0.1~0.05% of weight in system；Described 1,
3- glycidyl aoxidizes disiloxane and octamethylcy-clotetrasiloxane weight ratio are as follows: 34:1000.Reactional equation described above
Formula are as follows:
Wherein m=130
The target product α that step (3) obtains step (2), ω-glycidyl oxidation propyl dimethyl silicone polymer are added
To in the mixture of glucose methylamine and isopropanol, the structure of glucose methylamine are as follows:
Under the conditions of 60~85 DEG C of temperature, react 12~48 hours.Obtain product α, the ω-different hydroxypropyl of methylamino glucose
Aoxidize propyl dimethyl silicone polymer, reaction equation are as follows:
It is 40~70% that wherein isopropanol, which accounts for the total weight of reaction system, the glucose methylamine and α, ω-glycidyl
The molar ratio for aoxidizing propyl dimethyl silicone polymer is 2.0~2.2:1.
The target product α of step (3), the different hydroxypropyl of ω-methylamino glucose are aoxidized propyl poly dimethyl silicon by step (4)
Oxygen alkane is added acid and is uniformly mixed, then add α, ω-glycidyl polyethers, in temperature 60 under the conditions of 20~60 DEG C of temperature
Under the conditions of~85 DEG C, reacts 12~60 hours, then distill out isopropanol under the conditions of 85 DEG C~120 DEG C of temperature, obtain target
Product: the different hydroxypropyl of polyquaternary amine base glucose aoxidizes propyl polydimethylsiloxane polyether.Wherein the acid is HCl, HBr,
HI, CH3COOH, CH3CH2COOH, CH3C2H4COOH, one or more of mixtures, the weight being added are grape to lauric acid in the middle
The equimolar quantity of sugared methylamine.The wherein α, ω-glycidyl polyethers structure are as follows:A=2~6, b=15~40.Above-mentioned reaction equation is as follows:
Wherein A-=Cl-, Br-, I-, CH3COO-, C2H5COO-, C3H7COO-, laurate
N=130, a=2~6, b=15~40, m=2~100.
The different hydroxypropyl oxidation propyl dimethyl silicone polymer of above-mentioned α, ω-methylamino glucose and α, ω-glycidyl are poly-
The molar ratio of ether is 7:6~8:7, and wherein isopropanol accounts for system total weight 40%~70%.
The different hydroxypropyl of the target product polyquaternary amine base glucose of step (4) is aoxidized propyl polydimethylsiloxanes by step (5)
Alkane polyethers is uniformly mixed with nonionic emulsifier isomeric alcohol polyethenoxy ether, is then slowly diluted with water, and is finally adjusted with acetic acid
PH value, makes pH value value between 4.5~6.5, and it is poly- then to obtain the different hydroxypropyl oxidation propyl of target product polyquaternary amine base glucose
Dimethyl siloxane polyethers hand feel finishing agent.The hand feel finishing agent includes specifically following components by mass percentage: 40%
Polyquaternary amine base glucose silicone polyether, 2.5% ten carbon isomery alcohol polyoxyethylene -5,2.5% ten carbon isomery alcohol it is poly-
The acetic acid that the concentration of ethylene oxide -9,0.5% is 100%, surplus is water.It is denoted as hand feel finishing agent C.
Assessment of performance embodiment
In the present embodiment, the performance of above-mentioned hand feel finishing agent A~C is detected.
Final filming performance is detected first.Experiment condition specifically: glass surface ware, diameter 8cm, 105 DEG C of oven temperature
~110 DEG C, the time 2.5 hours, latex solids content was 45% or so, toasted lotion weight: 5g.Experimental result is see table 5.
The filming performance of the hand feel finishing agent A~C of the present invention of table 5..
In addition, applicant is also with 32s, the 40s looped fabric of combed cotton containing spandex thread is experimental subjects, product emulsion solid content
It is 45%, dosage 80g/l, pick-up 80%, 190 DEG C of setting temperature, speed 40m/min, retention time 40 seconds, after sizing sufficiently
Resurgence 2 hours, hydrophily, the feel of the cloth specimen after the test second generation, forth generation and hand feel finishing agent of the present invention arrangement are commented
It is fixed, yellowing-resistant, anti-phenol xanthochromia are tested, and obtain 6~table of table, 8 data.
Cloth specimen fluffy degree comparison of the table 6. after the second generation, forth generation and hand feel finishing agent A of the present invention arrangement
Cloth specimen pliability comparison of the table 7. after the second generation, forth generation and hand feel finishing agent B of the present invention arrangement
Cloth specimen smoothness comparison of the table 8. after the second generation, forth generation and hand feel finishing agent C of the present invention arrangement
By the experimental data of above-mentioned 5~table of table 8 it can be shown that in the present invention, passing through synthesis technology route and starting material
Selection, so that the apparent state of film forming of hand feel finishing agent of the present invention is from the liquid or hemicolloid state in currently available technology
It is transformed into solid-state or elastomer solid-state, so that fabric sense of touch " oiliness " is overweight after revolutionizing previous organic silicon emulsion arrangement,
So that unnatural, the uncomfortable technical problem of " viscous hand " personal clothing.Therefore, hand feel finishing agent of the present invention assigns again
The new sense of touch of fabric: dry and comfortable tack-free, dry and comfortable, natural fine and smooth pro-skin, silk quality are soft and smooth, while assigning cotton fiber fabric moment parent
Water, without hot xanthochromia, the beneficial function such as no phenol xanthochromia.Product of the present invention improves the surcharge of fabric.Product of the present invention is
Realize large-scale technology production.
The present invention is described by above-mentioned related embodiment, however above-described embodiment is only to implement example of the invention.
It must be noted that, it has been disclosed that embodiment be not limiting as the scope of the present invention.On the contrary, being contained in the spirit of claims
And range modification and impartial setting be included in the scope of the present invention.
Claims (11)
1. a kind of polyquaternary amine base glucose polydimethylsiloxane polyether, which is characterized in that the polyquaternary amine base glucose poly- two
Methylsiloxane polyethers is indicated with following general formula I:
Wherein, A-Selected from Cl-, Br-, I-, CH3COO-, C2H5COO-, C3H7COO-Or one of laurate；N be selected from 10~
1000 integer；A is the integer selected from 1~20；B is 1~60；M is the integer selected from 2~100.
2. a kind of preparation method of polyquaternary amine base glucose polydimethylsiloxane polyether as described in claim 1, feature
It is, the described method comprises the following steps:
Step 1. with 1,1,3,3- tetramethyldihydrogendisiloxane and allyl glycidyl ether for starting material, with the different of chloroplatinic acid
Propanol solution is catalyst, is reacted under the conditions of 70 DEG C~80 DEG C to obtain 1,3- glycidyl oxidation disiloxane；
The 1,3- glycidyl oxidation disiloxane and octamethylcy-clotetrasiloxane that step 2. is obtained with step 1 is startings
Object, using tetramethylammonium hydroxide as catalyst, under nitrogen protection under the conditions of 80~155 DEG C reaction to obtain α, ω-epoxy third
Base aoxidizes propyl dimethyl silicone polymer；
The α that step 3. is obtained with step 2, ω-glycidyl oxidation propyl dimethyl silicone polymer and glucose methylamine are starting
Object is reacted under the conditions of 60~85 DEG C of temperature in the presence of isopropanol to obtain α, the different hydroxypropyl oxidation of ω-methylamino glucose
Propyl dimethyl silicone polymer；
In the different hydroxypropyl oxidation propyl dimethyl silicone polymer of the α that step 4. is obtained to step 3, ω-methylamino glucose
After acid is added, α is added, ω-glycidyl polyethers reacts under the conditions of 60~85 DEG C in the presence of isopropanol, obtains target and produces
Object polyquaternary amine base glucose polydimethylsiloxane polyether.
3. preparation method as claimed in claim 2, which is characterized in that in the step 1, described 1,1,3,3- tetramethyl two
The molar ratio range of hydrogen disiloxane and allyl glycidyl ether is in 1:(2.1~4.0) between；The dosage of the catalyst
It is the 0.05%~0.1% of step 1 reaction system gross mass；Also, the aqueous isopropanol of the chloroplatinic acid as catalyst
Mass percentage concentration be 1%.
4. preparation method as claimed in claim 2, which is characterized in that in the step 2,1, the 3- glycidyl oxidation
The quality of disiloxane and octamethylcy-clotetrasiloxane is than range in (34~90): between 1000；The tetramethyl hydrogen-oxygen
The dosage for changing ammonium is the 0.05%~0.1% of step 2 reaction system gross mass.
5. preparation method as claimed in claim 2, which is characterized in that in the step 3, the α, ω-glycidyl oxygen
Change the molar ratio range of propyl dimethyl silicone polymer and glucose methylamine in 1.0:(2.0~2.2)；The isopropanol adds
Amount is the 40%~70% of step 3 reaction system gross mass.
6. preparation method as claimed in claim 2, which is characterized in that in the step 4, the α, ω-methylamino grape
The different hydroxypropyl oxidation propyl dimethyl silicone polymer of sugar and α, ω-glycidyl polyethers molar ratio range are in (0.5~2): 1；
The dosage of the isopropanol is the 40%~70% of step 4 reaction system gross mass；The dosage of the acid be with the α,
ω-glycidyl polyethers molal weight is equal.
7. preparation method as claimed in claim 6, which is characterized in that the acid is selected from HCl, HBr, HI, CH3COOH、
CH3CH2COOH、CH3C2H4One of COOH or lauric acid.
8. a kind of hand feel finishing agent, which is characterized in that the effective component of the hand feel finishing agent is poly- season described in claim 1
Ammonium glucose polydimethylsiloxane polyether.
9. hand feel finishing agent as claimed in claim 8, which is characterized in that the hand feel finishing agent includes by mass percentage:
The polyquaternary amine base glucose polydimethylsiloxane polyether 30~40%；
Nonionic emulsifier 68~46%；
Acetic acid 0.01~0.05%；
Surplus is water；Also, the pH value range of the hand feel finishing agent is between 4.5~6.5.
10. hand feel finishing agent as claimed in claim 9, which is characterized in that the nonionic emulsifier is isomery alcohol polyoxy second
Alkene ether.
11. hand feel finishing agent as claimed in claim 10, which is characterized in that the nonionic emulsifier is poly- selected from C8 isomery alcohol
Ethylene oxide ether, the mixing of one or more of C10 isomeric alcohol polyethenoxy ether or C13 isomeric alcohol polyethenoxy ether.
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| CN101497697A (en) * | 2008-07-11 | 2009-08-05 | 浙江传化股份有限公司 | Preparation of block water-soluble silicon oil |
| CN102558567A (en) * | 2011-12-10 | 2012-07-11 | 江阴市尼美达助剂有限公司 | Preparation method of quaternary copolymer block organic silicon oil |
| CN102617863A (en) * | 2012-03-30 | 2012-08-01 | 广东工业大学 | Preparation method of hydrophilic block polyether aminosilicone |
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| DE10325094B4 (en) * | 2003-06-03 | 2006-02-16 | Rudolf Gmbh & Co. Kg Chemische Fabrik | Preparations for the oil and water repellent finishing of fabrics and their use |
| DE102007020790B4 (en) * | 2007-05-03 | 2009-10-01 | Rudolf Gmbh & Co. Kg Chemische Fabrik | Fluorocarbon polymer-free preparations based on water and / or organic solvents and their use as a finish on fabrics and textile substrates obtained therefrom |
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| CN101497697A (en) * | 2008-07-11 | 2009-08-05 | 浙江传化股份有限公司 | Preparation of block water-soluble silicon oil |
| CN102558567A (en) * | 2011-12-10 | 2012-07-11 | 江阴市尼美达助剂有限公司 | Preparation method of quaternary copolymer block organic silicon oil |
| CN102617863A (en) * | 2012-03-30 | 2012-08-01 | 广东工业大学 | Preparation method of hydrophilic block polyether aminosilicone |
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